EP1457319B1 - Feuille multicouche et transparente en polyester biaxialement orientée, son procédé de fabrication et utilisation - Google Patents

Feuille multicouche et transparente en polyester biaxialement orientée, son procédé de fabrication et utilisation Download PDF

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Publication number
EP1457319B1
EP1457319B1 EP20040000702 EP04000702A EP1457319B1 EP 1457319 B1 EP1457319 B1 EP 1457319B1 EP 20040000702 EP20040000702 EP 20040000702 EP 04000702 A EP04000702 A EP 04000702A EP 1457319 B1 EP1457319 B1 EP 1457319B1
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EP
European Patent Office
Prior art keywords
film
base layer
layer
coating
weight
Prior art date
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Expired - Fee Related
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EP20040000702
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German (de)
English (en)
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EP1457319A1 (fr
Inventor
Herbert Dr. Professor Peiffer
Gottfried Dr. Hilkert
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Mitsubishi Polyester Film GmbH
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Mitsubishi Polyester Film GmbH
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/91—Product with molecular orientation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/259—Silicic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • Y10T428/31699—Ester, halide or nitrile of addition polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/31797—Next to addition polymer from unsaturated monomers

Definitions

  • the invention relates to a multilayer, transparent, biaxially oriented polyester film having at least one base layer B made of a thermoplastic polyester, at least one cover layer A coextruded on the base layer B and at least one acrylate-containing layer D.
  • the invention further relates to a method for producing the film and its use.
  • Biaxially oriented polyester films bearing a continuous coating on at least one of their two surfaces are known in the art. Also known in the prior art are biaxially oriented polyester films, which are characterized by very good optical properties.
  • the EP-A-0 144 978 describes an oriented film made of thermoplastic material, which carries on at least one of its two surfaces, a continuous polyester coating, which is applied as an aqueous dispersion on the film.
  • the polyester coating consists of a condensation product of various polyesters capable of forming polyesters such as isophthalic acid, aliphatic dicarboxylic acid, sulfomonomers and aliphatic or cycloaliphatic glycols.
  • the film is characterized in particular by a good adhesion to metals.
  • a disadvantage of the film are its optical properties, such as transparency or gloss. Due to this disadvantage, this film is no longer used in high-quality packaging applications.
  • EP-A-0 144 948 describes an oriented film made of thermoplastic material, which carries on at least one of its two surfaces, a continuous crosslinked acrylate-containing coating, which is applied as an aqueous dispersion on the film.
  • the acrylate-containing coating consists of copolymers with at least 50% by weight of acrylic and / or methacrylic monomers, 1-15% by weight of monomers containing a functional group which is capable of undergoing intermolecular crosslinking in the copolymerized state under the action of elevated temperatures, and one or more monoethylenically unsaturated, halogen-free monomers in an amount up to 49 wt .-%, wherein the percentages are based on the total weight of the adhesive layer forming copolymer ,
  • the film has good printability and can be sterilized.
  • a disadvantage of the film are its optical properties, such as transparency or gloss. Due to this disadvantage, this film is no longer used in high-quality packaging applications.
  • the EP-A-0 903 221 relates to an at least three-layer, biaxially oriented polyester film which has very good processing properties compared to films of the prior art improved optical properties and which has a good oxygen barrier after metallization or after their coating with oxidic materials, and of at least one base layer B and Cover layers A and C applied to this base layer are constructed, these cover layers having a defined number of elevations with a defined height and a defined diameter.
  • EP-A further relates to a process for producing the film and its use. The running behavior of this film, especially in high-speed packaging machines is still in need of improvement. Further improvement is the roll presentation of films produced in this way. A very good role presentation is needed in particular in the metallization or in the processing of the films to hot stamping foils.
  • EP-A-1197328 describes a co-extruded, biaxially oriented film having at least one matte surface and containing a base layer of a thermoplastic polyester and at least one matte top layer of a blend of PET and an isophthalic acid copolymer.
  • the film should be easy to print, especially with nitro-cellulose colors.
  • the film should be sterilized.
  • film waste which is obtained as a regenerate, can be returned to the extrusion and film production in an amount of up to 60% by weight, based on the total weight of the film, without causing physical damage Properties of the film are appreciably adversely affected.
  • the film has at least two layers and then consists of the base layer B and the cover layer A.
  • One of these two layers carries the thoroughly crosslinked acrylic coating D, which is applied to the film as an aqueous dispersion.
  • the acrylic coating D is preferably applied to the base layer B which contains only a small amount of fillers.
  • the film according to the present invention has a three-layer structure and then comprises a base layer B and two outer layers A and C.
  • the acrylic coating D is applied to that cover layer which contains fewer fillers than the other cover layer.
  • the film according to the present invention is constructed in three layers and then comprises a base layer B and the two outer layers A and C, wherein the two outer layers A and C are the same formulation.
  • This embodiment is referred to as ABA variant of the three-layered embodiment.
  • the base layer B of the film preferably contains at least 90% by weight of thermoplastic polyester.
  • polyesters which consist of at least 90 mol%, preferably at least 95 mol%, of ethylene glycol and terephthalic acid units or of ethylene glycol and naphthalene-2,6-dicarboxylic acid units.
  • the remaining monomer units are derived from other aliphatic, cycloaliphatic or aromatic diols or dicarboxylic acids, as they may also occur in layer A or layer C.
  • Suitable other aliphatic diols are, for example, diethylene glycol, triethylene glycol, aliphatic glycols of the general formula HO- (CH 2 ) n -OH, where n is a represents integer from 3 to 6 (especially propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol and hexane-1,6-diol) or branched aliphatic glycols of up to 6 carbon -atoms.
  • cycloaliphatic diols mention may be made of cyclohexanediols (in particular cyclohexane-1,4-diol).
  • Suitable other aromatic diols correspond, for example, to the formula HO-C 6 H 4 -XC 6 H 4 -OH, where X is -CH 2 -, -C (CH 3 ) 2 -, - C (CF 3 ) 2 -, -O -, -S- or -SO 2 - stands.
  • bisphenols of the formula HO-C 6 H 4 -C 6 H 4 -OH are also very suitable.
  • aromatic dicarboxylic acids are preferably benzenedicarboxylic acids, naphthalenedicarboxylic acids (for example naphthalene-1,4- or 1,6-dicarboxylic acid), biphenyl-x, x'-dicarboxylic acids (in particular biphenyl-4,4'-dicarboxylic acid), diphenylacetylene-x, x ' dicarboxylic acids (especially diphenylacetylene-4,4'-dicarboxylic acid) or stilbene-x, x'-dicarboxylic acids.
  • cycloaliphatic dicarboxylic acids mention may be made of cyclohexanedicarboxylic acids (in particular cyclohexane-1,4-dicarboxylic acid).
  • aliphatic dicarboxylic acids the (C 3 -C 19) alkanedioic acids are particularly suitable, it being possible for the alkane part to be straight-chain or branched.
  • the preparation of the polyesters may e.g. done after the transesterification process. It is based on dicarboxylic acid esters and diols, which are reacted with the usual transesterification catalysts, such as zinc, calcium, lithium, magnesium and manganese salts. The intermediates are then polycondensed in the presence of commonly used polycondensation catalysts, such as antimony trioxide or titanium salts.
  • the preparation can also be carried out by the direct esterification process in the presence of polycondensation catalysts. It starts directly from the dicarboxylic acids and diols.
  • the same polymers can be used for the outer layers A and C as for the base layer B.
  • other materials can be contained in the outer layers A and C, in which case the outer layers A and C are preferably made of such polymers, the ethylene isophthalate Units and / or ethylene-2,6-naphthalate units and ethylene terephthalate units contain. Up to 30 mol% of the polymers may consist of other comonomers.
  • the coated outer layer A or C may contain a mixture of polymers, a copolymer or a homopolymer of ethylene isophthalate units.
  • an intermediate layer can also be present between the base layer B and the outer layer (s) A and C. It may consist of the polymers described for the base layer B. In a particularly preferred embodiment, it consists of the polyester used for the base layer B.
  • the intermediate layer may also contain the conventional additives described.
  • the thickness of the intermediate layer is generally greater than 0.3 ⁇ m and is preferably in the range from 0.5 to 15 ⁇ m, in particular from 1.0 to 10 ⁇ m.
  • the thickness of the cover layer (s) A and C is generally greater than 0.1 microns and is preferably in the range of 0.2 to 5 .mu.m, in particular from 0.2 to 4 microns, wherein the outer layers A and C are the same or different can be fat.
  • the total thickness of the polyester film according to the invention can vary within wide limits and depends on the intended use. It is 4 to 50 microns, preferably 5 to 40 microns, more preferably 6 to 30 microns, wherein the base layer B has a proportion of preferably 40 to 95% of the total thickness of the film.
  • the base layer B and the other layers may additionally contain conventional additives such as stabilizers, antiblocking agents and other fillers. They are expediently added to the polymer or the polymer mixture before melting.
  • Stabilizers used are, for example, phosphorus compounds, such as phosphoric acid or phosphoric acid esters.
  • Typical antiblocking agents are inorganic and / or organic particles, for example calcium carbonate, amorphous silica, fumed silica, spherical silica particles, talc, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminum oxide, lithium fluoride , Calcium, barium, zinc or manganese salts of the dicarboxylic acids used, carbon black, titanium dioxide, kaolin or crosslinked polymer particles, eg Polystyrene or acrylate particles.
  • the particles can be added to the polymers of the individual layers of the film in the respectively advantageous concentrations, for example as a glycolic dispersion during the polycondensation or via masterbatches during the extrusion.
  • a detailed description of the antiblocking agents can be found, for example, in US Pat EP-A-0 602 964 ,
  • Particles which satisfy this description are particularly suitable for the production of films which have very good optical properties such as high gloss and should have low turbidity.
  • the cover layer (s) A and C of the film contain a pigment system in which the dispersion of the diameter d (expressed by the SPAN 98) is less than or equal to 1.9, preferably less than or equal to 1.7.
  • the pigment concentration in the outer layer A is between 500 and 2500 ppm, preferably between 600 and 2200 ppm and more preferably between 700 and 1900 ppm.
  • the film is constructed in three layers and then contains the additional top layer C.
  • the pigment concentration in the top layer C is then between 50 and 2500 ppm, preferably between 100 and 2300 ppm and most preferably between 150 and 2100 ppm. It depends in particular on the desired processing behavior of the film.
  • the type of pigment (s), the pigment concentration (s) and the particle concentration (s) as well as the layer thickness ratios are / are preferably chosen such that good optics, as well as good manufacturability and processability of the film are present.
  • the coating D on the finished film has a thickness of 5 to 2000 nm, preferably 10 to 500 nm, in particular 20 to 200 nm.
  • the coating D is preferably applied in-line, ie during the film production process, expediently before the transverse stretching.
  • Particularly preferred is the application of the coating D by means of the "reverse gravure-roll coating” process, in which the coatings D can be applied very homogeneously in layer thicknesses up to 100 nm.
  • the application of the coating D by the Meyer-Rod process which can be used to achieve higher coating thicknesses.
  • the coating D is preferably applied as a solution, suspension or dispersion, more preferably as an aqueous solution, suspension or dispersion.
  • Said coating D gives the film surface or the film the desired functions (low coefficient of friction, good processability, good role presentation, low static charge) and possible other functions.
  • the film may thereby be better printable or have improved flavor barrier or allow adhesion to materials that would otherwise not adhere to the film surface (eg, photographic emulsions).
  • the substances / compositions mentioned are applied as dilute solution, emulsion or dispersion, preferably as aqueous solution, emulsion or dispersion, to one or both surfaces of the film, and then the solvent or dispersant is volatilized.
  • the temperature treatment in the transverse extension and subsequent heat-fixing is usually sufficient to volatilize the solvent or dispersant and to dry the coating D.
  • the aqueous dispersion contains acrylic copolymers.
  • the copolymers preferably used consist essentially of at least 50 wt .-% of one or more polymerized acrylic and / or methacrylic monomers and 1 to 15 wt .-% of a copolymerizable comonomer in the copolymerized state under the action of elevated temperature, optionally without the addition of a separate resinous vehicle, capable of forming intermolecular crosslinks.
  • the acrylic component of the copolymers is preferably present in an amount of from 50 to 99% by weight and preferably consists of an ester of acrylic or methacrylic acid, in particular an alkyl ester whose alkyl group contains up to ten carbon atoms, such as, for example, the methyl , Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, hexyl, 2-ethylhexyl, heptyl and n-octyl groups.
  • an ester of acrylic or methacrylic acid in particular an alkyl ester whose alkyl group contains up to ten carbon atoms, such as, for example, the methyl , Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, hexyl, 2-ethylhexyl,
  • Acrylic copolymers the derived from a lower alkyl acrylate (C, to C 4 ), in particular ethyl acrylate, together with a lower alkyl methacrylate give a particularly good adhesion between the polyester film and applied therefrom reprographic coatings and matte coatings.
  • adhesion promoter copolymers composed of an alkyl acrylate, for example ethyl acrylate or butyl acrylate, together with an alkyl methacrylate, for example methyl methacrylate, in particular in equal molar proportions and in a total amount of from 70 to 95% by weight.
  • the acrylate comonomer of such acrylic / methacrylic combinations is preferably present at a level of from 15 to 65 mole percent, and the methacrylate comonomer is preferably present at a level generally greater by 5 to 20 mole percent than the proportion of acrylate comonomer.
  • the methacrylate is preferably contained in a proportion of 35 to 85 mol% in the combination.
  • suitable comonomers may be used to form crosslinks, for example N-methylolacrylamide, N-methylolmethacrylamide and the corresponding ethers; Epoxy materials such as glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether; Carboxyl group-containing monomers such as crotonic acid, itaconic acid or acrylic acid; Anhydrides such as maleic anhydride; Hydroxyl group-containing monomers such as itaconic anhydride; Hydroxyl group-containing monomers such as allyl alcohol and hydroxyethyl or hydroxypropyl acrylate or methacrylate; Amides such as acrylamide, methacrylamide or maleic acid amide and isocyanates such as vinyl isocyanate or allyl isocyanate.
  • Epoxy materials such as glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether
  • N-methylolacrylamide and N-methylolmethacrylamide are preferred, primarily because copolymer chains containing one of these monomers, under the action of elevated temperatures, allow condensation with one another and thus formation of the desired intermolecular crosslinks are.
  • the optionally desired solvent resistance of the preferred acrylate coating can also be achieved by the presence of a foreign crosslinking agent, such as a melamine or urea-formaldehyde condensation product. Will not solvent resistance needed, can be dispensed with crosslinking agent.
  • the coating D can be applied to the film on one or both sides. However, it is also possible to provide only one side of the film with the coating D according to the invention and to apply another coating to the opposite side.
  • the coating formulation may contain known additives such as antistatics, wetting agents, surfactants, pH regulators, antioxidants, dyes, pigments, anti-blocking agents such as colloidal SiO 2 , etc. Usually, it is convenient to incorporate a surfactant to enhance the ability of the aqueous coating Wetting of the carrier film made of polyester to increase.
  • the base layer B containing less pigment is preferably coated with the aqueous acrylic dispersion.
  • the cover layer A may also have the acrylic coating D.
  • the base layer B and the two outer layers A and C preferably that layer receives the acrylic coating D which has a lower concentration of antiblocking agent.
  • the property improvements with regard to processing behavior and role presentation are particularly pronounced.
  • the other outer layer or both outer layers A and C may also have the acrylic coating D.
  • the acrylic coating D can be applied selectively to one or the other side without This results in decisive advantages or disadvantages.
  • both outer layers A and C may have the acrylic coating D.
  • the coefficient of friction (COF) of the film side carrying the acrylic coating D is particularly low. On this (coated side) of the film, the coefficient of friction is then less than 0.5, preferably less than 0.45 and particularly preferably less than 0.4. The low coefficient of friction contributes significantly to a good processing behavior of the film and to a good role presentation.
  • a particular advantage is that the production costs of the film according to the invention are only insignificantly higher than those of a film of standard polyester raw materials. However, the processing and use-relevant properties of the film according to the invention are significantly improved compared to films of the prior art.
  • the regenerated material can be reused to a proportion of up to 60% by weight, preferably from 10 to 50% by weight, in each case based on the total weight of the film, without the physical properties of the film are appreciably adversely affected.
  • the granules of polyethylene terephthalate and the masterbatch of polyethylene terephthalate / antiblocking agent in the desired mixing ratio are expediently fed directly to the extruder (s).
  • the materials can be melted at about 300 ° C and extruded.
  • the polymers for the base layer B are suitably fed via a further extruder. Existing foreign bodies or impurities can be filtered off from the polymer melt.
  • the melts are then formed into flat melt films in a multi-layer die and stacked one on top of the other. Subsequently, the multi-layer film is drawn off and solidified with the aid of a cooling roller and optionally further rollers.
  • the biaxial stretching is generally carried out sequentially. It is preferably stretched first in the longitudinal direction (i.e., in the machine direction) and then in the transverse direction (i.e., perpendicular to the machine direction). This leads to an orientation of the molecular chains within the polyester.
  • the stretching in the longitudinal direction can be carried out with the aid of two rolls rotating at different speeds according to the desired stretch ratio. For cross-stretching you generally use a corresponding clip frame.
  • the temperature at which the stretching is carried out may vary within a relatively wide range and depends on the desired properties of the film.
  • the stretching is carried out in the longitudinal direction at 80 to 130 ° C and the transverse extension at 90 to 150 ° C.
  • the longitudinal stretching ratio is in the range from 2.5: 1 to 6: 1, preferably from 3: 1 to 5.5: 1.
  • the transverse stretching ratio is in the range from 3.0: 1 to 5.0: 1, preferably from 3.5: 1 to 4.5: 1.
  • the film is kept at a temperature of 150 to 250 ° C over a period of about 0.1 to 10 seconds. Subsequently, the film is wound in the usual manner.
  • the film coated with the above-described acrylic polymer shows very good handling, very good winding properties and very good processing behavior.
  • the film according to the present invention is characterized by excellent optical properties, excellent further processing and by excellent roll presentation. Due to its very good handling and due to its very good processing properties, the film is particularly suitable for processing on high-speed machines.
  • the film of the present invention is also characterized by high gloss and low haze over prior art films.
  • the gloss of the outer layer A (and optionally the outer layer C) is greater than 180.
  • the gloss of this side (s) is more than 190 and in a particularly preferred embodiment more than 200.
  • the film with this gloss is particularly suitable for printing or for metallization.
  • the high gloss of the film is transferred to the pressure or the applied metal layer and thus gives the final product the desired promotional effect.
  • the haze of the film is less than 2.5%, preferably less than 2.2%, and more preferably less than 1.9%.
  • waste material can be re-fed to the extrusion as regenerate in an amount of up to 60% by weight, based on the total weight of the film, without the physical properties of the film being appreciably negative to be influenced.
  • the film according to the invention is outstandingly suitable for packaging foodstuffs of all kinds.
  • Table 1 summarizes the most important film properties according to the invention once again.
  • Table 1 Inventive area Prefers Especially preferred unit measurement method Cover layer A Antiblocking concentration 500 to 2500 600 to 2200 700 to 1900 ppm Diameter of the 10 to 60 nm and / or 10 to 60 nm and / or 10 to 60 nm and / or antiblock 1.0 to 5.0 ⁇ m 1.0 to 5.0 ⁇ m 1.0 to 5.0 ⁇ m SPAN 98 of the ⁇ 1.9 ⁇ 1.8 ⁇ 1.7 Particle diameter film properties shine > 180 > 190 > 200 DIN 67 530 cloudiness ⁇ 2.5 ⁇ 2.2 ⁇ 1.9 % ASTM-D 1003-52 Coefficient of friction (COF) of the acrylic coated side against itself in the most preferred ABA variant ⁇ 0.5 ⁇ 0.45 ⁇ 0.4 DIN 53 375
  • the standard viscosity SV (DCE) is measured, based on DIN 53726, in dichloroacetic acid.
  • the friction was determined according to DIN 53 375.
  • the coefficient of sliding friction was measured 14 days after production.
  • the haze of the film was measured according to ASTM-D 1003-52. Hölz's haze measurement was carried out according to ASTM-D 1003-52, but to measure the optimum measuring range was measured on four superimposed film layers and instead of a 4 ° -poch screen a 1 ° slit was used.
  • the gloss was determined according to DIN 67 530.
  • the reflector value was measured as an optical parameter for the surface of a film. Based on the standards ASTM-D 523-78 and ISO 2813, the angle of incidence was set at 20 ° or 60 °. A light beam strikes the flat test surface under the set angle of incidence and is reflected or scattered by it. The light rays incident on the photoelectronic receiver are displayed as a proportional electrical quantity. The measured value is dimensionless and must be specified with the angle of incidence.
  • the determination of the mean particle diameter d 50 was carried out by laser on a Malvern MasterSizer according to the standard method (other measuring devices are eg Horiba LA 500 or Sympathec Helos, which use the same measuring principle). The samples were placed in a cuvette with water and then placed in the meter. The measuring process is automatic and includes the mathematical determination of the d 50 value.
  • the d 50 value is determined from the (relative) cumulative particle size distribution curve: the point of intersection of the 50% ordinate value with the cumulative curve immediately gives the desired d 50 value on the abscissa axis.
  • the determination of the SPAN 98 was carried out with the same measuring instrument as described above for the determination of the mean diameter d 50 .
  • d 98 and d 10 are again based on the (relative) cumulative curve of the particle size distribution.
  • the point of intersection of the 98% ordinate value with the cumulative curve immediately gives the desired d 98 value on the abscissa axis and the point of intersection of the 10% ordinate value of the cumulative curve immediately gives the desired d 10 value on the abscissa axis.
  • the coating D according to the invention contains a 4.5% strength by weight solution of a latex consisting of a copolymer of 60% by weight of methyl methacrylate, 35% by weight of ethyl acrylate and 5% by weight of N-methylolacrylamide and of a surfactant. It the coating of the cover layer A of the film according to the present invention was carried out.
  • Chips of polyethylene terephthalate were dried at 160 ° C. to a residual moisture content of less than 50 ppm and fed to the base layer B extruder. Also, chips of polyethylene terephthalate and a filler were fed to the extruders for the outer layers A and C.
  • a uniaxially oriented film was obtained, which was corona treated and coated by the reverse gravure process with the dispersion described above.
  • the dry weight of the coating was about 0.035 g / m 2 (based on the biaxially stretched film). The thus stretched film was stretched in the transverse direction to a transparent three-layer film with ABC structure and a total thickness of 12 microns.
  • the two outer layers had a thickness of 1.5 microns each.
  • Example 2 Analogously to Example 1, a three-layer ABC film with a total thickness of 12 ⁇ m was produced by coextrusion. Only the composition of the two outer layers A and C was changed. As in the two previous examples, the coating of the cover layer A of the film according to the present invention was carried out.
  • Example 1 was worked up, but now the film did not contain coating D. Although the film has a good appearance, it was significantly worse in processing behavior. In addition, the winding quality left a lot to be desired.
  • Table 2 example film thickness film structure layer thicknesses Pigments in the layers average pigment diameter pigment concentrations microns ABC ⁇ m A B C A B ⁇ m C A B ppm C example 1 12 DABA 1.5 / 9.0 / 1.5 Sylobloc 44 H none Sylobloc 44 H 2.5 2.5 800 0 800
  • Example 2 12 DABA 1.5 / 9.0 / 1.5 Sylysia 300 none Sylysia 300 2.5 2.5 800 0 800 Aerosil TT 600 Aerosil TT 600 0.04 0.04 800 0 800
  • Example 3 12 DABC 1.5 / 9.0 / 1.5 Sylobloe 44 H none Sylobloc 44 H 2.5 2.5 200 0 1200 Aerosil TT 600 Aerosil TT 600 0.04 0.04 200 0 1200
  • Example 4 12 DABA 1.5 / 9.0 / 1.5 Sylysi

Landscapes

  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (9)

  1. Feuille en polyester, orientée biaxalement, transparente, coextrudée et comprenant d'au moins deux couches, avec au moins une couche de base B contenant au moins 80 % en poids de polyester thermoplastique, au moins une couche de finition A qui est coextrudée sur la couche de base B et au moins un revêtement acrylique D, caractérisée en ce que
    a) les charges contenues dans la couche de base B contient des charges qui sont uniquement issues de la régénération de chutes de coupe récupérées pour être introduites dans la couche de base B ;
    b) la couche de finition A contient des charges en une quantité de 500 à 2500 ppm, par rapport au poids de la couche de finition A ;
    c) les charges sont essentiellement composées de SiO2, le diamètre moyen de particules d50 se situant entre 10 et 60 nm et/ou entre 1,0 et 1,5 µm ; et que
    d) au moins une des deux faces de la feuille est pourvue d'un revêtement acrylique D continu et réticulé, qui est déposé sur la feuille sous forme de dispersion aqueuse.
  2. Feuille selon la revendication 1, caractérisée en ce qu'elle comporte trois couches et en ce qu'elle est constituée de la couche de base A et des couches de finition A et C sur les deux faces de la couche de base B.
  3. Feuille selon la revendication 1, caractérisée en ce qu'elle comporte trois couches et en ce qu'elle est constituée de la couche de base B et des couches de finition A et C, avec A = C, sur les deux faces de la couche de base B.
  4. Feuille selon une ou plusieurs des revendications 1 à 3, caractérisée en ce que la couche de finition coextrudée A et, le cas échéant, la couche de finition coextrudée C contiennent des charges dont le diamètre des particules d présente une variance, exprimée comme SPAN98, inférieure ou égale à 1,9.
  5. Feuille selon une ou plusieurs des revendications 1 à 4, caractérisée en ce que le revêtement acrylique D contient un copolymère en émulsion à base d'acrylate d'alkyle et de méthacrylate d'alkyle, dont le comonomère d'acrylate est présent dans une proportion comprise entre 15 et 65 % molaires et le comonomère de méthacrylate dans une proportion comprise entre 35 et 85 % molaires, par rapport à la quantité totale du copolymère d'émulsion, d'autres comonomères appropriés comme le N-méthyloacrylamide ou le N-méthylométhacrylamide pouvant également être présents pour former des réticulations.
  6. Procédé de fabrication d'une feuille selon une ou plusieurs des revendications 2 à 5, comprenant les étapes suivantes :
    - réalisation par coextrusion d'une feuille comportant plusieurs couches et constituée d'une couche de base B ainsi que d'une couche / de couches finition A et, le cas échéant, C ;
    - orientation biaxiale de la feuille, d'abord dans le sens longitudinal puis dans le sens transversal ;
    - enduction de la feuille avec le revêtement acrylique réticulant D, de préférence après la première étape d'orientation et avant la deuxième étape d'orientation ;
    - thermofixage de la feuille orientée.
  7. Procédé selon la revendication 6, caractérisé en ce qu'on ajoute à la couche de base B une quantité pouvant atteindre 60 % en poids, par rapport au poids de la couche de base, de chutes de coupes régénérées.
  8. Utilisation d'une feuille selon une ou plusieurs des revendications 1 à 5 pour une impression et/ou une métallisation.
  9. Utilisation d'une feuille selon une ou plusieurs des revendications 1 à 5 pour emballer des aliments et des produits de consommation.
EP20040000702 2003-01-20 2004-01-15 Feuille multicouche et transparente en polyester biaxialement orientée, son procédé de fabrication et utilisation Expired - Fee Related EP1457319B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2003101786 DE10301786A1 (de) 2003-01-20 2003-01-20 Mehrschichtige transparente, biaxial orientierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10301786 2003-01-20

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EP1457319A1 EP1457319A1 (fr) 2004-09-15
EP1457319B1 true EP1457319B1 (fr) 2007-06-27

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US (1) US7094465B2 (fr)
EP (1) EP1457319B1 (fr)
JP (1) JP2004224047A (fr)
KR (1) KR20040067890A (fr)
DE (2) DE10301786A1 (fr)

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Also Published As

Publication number Publication date
DE10301786A1 (de) 2004-07-29
US20040146724A1 (en) 2004-07-29
US7094465B2 (en) 2006-08-22
JP2004224047A (ja) 2004-08-12
EP1457319A1 (fr) 2004-09-15
KR20040067890A (ko) 2004-07-30
DE502004004161D1 (de) 2007-08-09

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